Catalyst and hydrocarbon conversion therewith



United States Patent O.

CATALYST AND HYDROCARBON CONVERSION THEREWITH Henry E. Reif, DrexelHill, and Herbert L. Johnson,

Media, Pa., assignors to Sun Oil Company, Philadelphia, Pa., acorporation of New Jersey No Drawing. Application April-29, 1955 SerialNo. 505,046

20 Claims. (Cl. 208-110) This invention relates to catalyticcompositions elfective in catalytic processes for convertinghydrocarbons. More particularly, the invention relates to new andimproved inexpensive catalytic compositions, their preparation, and toprocesses for using the new catalysts such as processes for removingnon-hydrocarbons from mixtures thereof with hydrocarbons and forconverting heavy hydrocarbons to relatively low, boiling hydrocarbons.

Heavy hydrocarbon materials such as residues from petroleum crackingoperations, reduced heavy crude oil, still tars, and the like, are oflittle Value. Processes for converting such materials to more valuablelower boiling products have been described. Such processes generallyinvolve contacting the hydrocarbon material with hydrogen and a crackingor hydrogenation catalyst at high temperature and high pressure, thepressure usually being of a magnitude of about 3000 p.s.i.g. or higher.These processes generally require special, expensive catalysts, andsuffer from one or more other drawbacks, such as poor yields of thedesired distillate liquid products, excessive coke formation resultingin plugged equipment and other ditliculties, and high yields of dry gas.v

An especially serious drawback of processes heretofore used is thedegradation of the relatively high boiling products of the process sothat they are unsuitable, or at least less suitable, for use inrecycling to the process. By degradation is meant the conversion of aportion of the relatively high boiling materials of the charge stock toother relatively high boiling materials which, when again used in theprocess such as by recycling, are converted to coke. Degradation alsoincludes concentrating such high boiling materials, which are convertedto coke on reuse, in the recycle fraction. The Ramsbottom carbon residuemethod (ASTM D524-42) of evaluating the coke forming tendencies of boththe charge stock and recycle stock of the process provides a measure ofthe degradation of the relatively high boiling materials. Thus, when theRamsbottom carbon residue of the recycle stock from the process isgreater than the Ramsbottorn carbon residue of the charge stock, therecycle stock has been degraded and its reuse in the process results inthe formation of relatively large quantities of coke. Conversely, whenthe Ramsbottom carbon residue of the recycle stock is less than theRamsbottom carbon residue of the charge stock, the materials of therecycle stock have been upgraded and their reuse in the process resultsin a decrease in coke formation. Upgrading the recycle stock permitsrecycling to substantial extinction to form relatively low boilinghydrocarbons as the sole products of the process.

An object of the present invention is to provide new and improvedinexpensive catalytic compositions effective for convertinghydrocarbons. A further object is to provide a process for preparing thenew catalytic compositions of the invention. Another object is toprovide a process for converting heavy hydrocarbon materials torelatively low boiling hydrocarbon products. A particular object is toprovide a hydrocracking process for converting residual oils todistillate products in good yields, using GENERAL New catalyticcompositions have been discovered which give improved results inconverting hydrocarbons. The

new catalytic compositions comprises regenerated spent clay havingdeposited thereon as an essential ingredient a minor quantity ofmolybdic oxide. Preferably one other oxide of a metal from group VI(B)or group VIII of the periodic table is also deposited on the regeneratedspent clay. The new catalyst can thus advantageously comprise molybdicoxide and tungstic oxide deposited on regenerated spent clay. Ifdesired, still another metal oxide, conveniently designated as apromoting oxide, is combined therewith with good results, this latteroxide also preferably being from group VI(B) or VIII of the periodictable. A preferred catalytic composition may thus consist of regeneratedspent clay having deposited thereon molybdic oxide, another oxide of ametal of group VI(B) or VIII such as tungstic oxide, and prefer ably anoxide of still another metal, also preferably from group VI( B) or VIII,such as an oxide of chromium, iron, cobalt or nickel, but oxides ofother metals may be substituted therefor with good results, such as theoxides of zinc, manganese, zirconium or vanadium. When three metaloxides are deposited on regenerated spent clay toform a preferredcatalytic composition in accordance with the invention, the promotingoxide must be an oxide other than the required molybdic oxide and mustbe an oxide different from the oxide selected from the oxides of themetals of groups VI(B) and VIII, although it may be i also selected fromthe same groups.

It is essential that the metal oxide constitutents of the composition bepresent within narrowly defined ranges as hereinafter described.

The reactions involved in the preferred process employing the novelcatalysts of the invention are primarily the cracking of the relativelyhigh boiling hydrocarbon materials to lower boiling hydrocarbonmaterials and the hydrogenation of unsaturated hydrocarbons to saturatedhydrocarbons. The overall process, therefore, can conveniently bedesignated as hydrocracking. Reaction variables used in thehydrocracking process are described hereinafter.

The new catalytic compositions of the invention may be prepared by avariety of means, the general techniques of which are known in the art.It is of primary importance that the limits on the ranges of componentspresent in the catalytic composition be observed as hereinafterdiscussed.

THE CATALYST combinations thereof, which have been employed for thetreating of hydrocarbons by contact therewith, such as in processes fordecolorization of mineral oils, until their adsorbent capacity has beensubstantially consumed, and which have thereafter been separated fromthe body of oil and-oil adhered thereto has been removed by burning.

' Patented Oct. 13, 1959 aeoaess 3 I a The resulting regenerated spentclay should contain from 0.5% to 4%, and preferably from 1% to 2% byweight carbon. Such spent clay has heretofore provided a disposalproblem in petroleum refineries, and the use of this inexpensivematerial for preparing inexpensive but highly effective catalysts is asubstantial advantage of the invention.

Regenerated spent clay is an essential constituent of the catalyticcompositions of the invention and other materials, such as silica,alumina, mixtures of silica and alumina such as synthetic mixtures,carbon, bauxite, and the like, cannot be substituted therefor. Naturaladsorbent clays that give good results include, for example, kaolin,fullers earth, attapulgite and the montmorrilonite clays includingbentonite. The natural adsorbent clay may have been activated, such asby treatment with a mineral acid such as hydrochloric acid or sulfuricacid, prior to its use in the hydrocarbon treatment process, and goodresults obtained therewith in the present invention. It is not known whyregenerated spent clay is remarkably effective, when combined withcertain metal oxides, in converting hydrocarbons. It is believed thatthe prior use of the adsorbent clay in a hydrocarbon treating process,followed by burning adhered oil therefrom leaving deposited on the clayfrom about 0.5 to 4% by weight carbon, and usually from about 1 to 2% byweight carbon, adjusts the surface characteristics, such as the surfacearea including pore diameter, of the clay so that it is an especiallyeffective component of the present catalytic compositions.

The quantity of molybdic oxide deposited on the regenerated spent claymust be within the range of from 0.2 to 5% by weight. At quantitiesbelow 0.2% sub stantial conversion of heavy hydrocarbon materials tolighter boiling materials requires relatively high temperatures andresults in excessive coke formation, and in the degradation of therecycle stock of the process. At concentrations above 5% by weight,prohibitively high yields of dry gas, an undesired product, are obtainedfrom the process. When used, the other oxide of a metal selected fromthe group consisting of groups VI(B) and VIII of the periodic table,which is preferably tungstic oxide, may be present in a concentration upto 5% by weight. With a concentration of such other oxide above 5% byweight, substantially the same difficulties are observed as when thequantity of molybdic oxide is above the stated range therefor.Remarkably good results are obtained when substantially equalquantities, within the stated range, of molybdic oxide and the othermetal oxide, preferably tungstic oxide, are deposited on regeneratedspent clay. When at promoting oxide is employed, a quantity sufficientto enhance the activity of the catalyst should be used, such quantitybeing a promoting quantity. This quantity will generally besubstantially equivalent to the quantities of molybdic oxide andtungstic oxide used, i.e., a quantity sufiicient for the metal of thepromoting oxide to react stoichiometrically with both the tungsten andmolybdenum oxides. For example with C0 0 as the promoting oxide, thequantity of the water soluble compound of cobalt used to impregnate theregenerated spent clay, as hereinafter described, should be such thatthe quantity of the cobalt is just sulficient to react with themolybdenum compound to form cobalt molybdate and with the tungstencompound to form cobalt tungstate. It appears immaterial whether suchreaction, in whole or in part, actually occurs, and hence the promotingmaterial is conveniently described as the metal oxide although it isrealized that the metal thereof may at least in part be combined incomplex compounds with the tungsten and molybdenum oxides. The promotingoxide is preferably an oxide of chromium, iron, cobalt, nickel,manganese or me.

To illustrate specific catalytic compositions in accordance with theinvention, regenerated spent clay having deposited thereon 0.5% byweight M00 and 0.5% by weight W0 gives good results. Deposition of apromoting quantity of an oxide of cobalt, nickel, manganese or zinc onthis catalytic composition is advantageous. An oxide of chromium can besubstituted for tungsten oxide in the above compositions and goodresults obtained therewith.

PREPARATION OF CATALYST Although the catalytic compositions of thepresent invention may be prepared by various means, it is preferred toemploy aqueous solutions of water soluble compounds of the metals whoseoxides are desired. Such aqueous solutions are used to impregnate theregenerated spent clay, the concentration of the water soluble compoundand quantity used to impregnate the clay being such that the resultingconcentration of metal oxide will be within the stated ranges. Separatesolutions of water soluble compounds of the metals whose oxides aredesired in the final catalytic composition may be used, or in a singlesolution containing two or more water soluble compounds, such as watersoluble compounds of molybdenum, tungsten and cobalt, may be used. Whenseparate solutions are employed, impregnation may be done in anysuccession desired, but it is preferred to impregnate the regeneratedspent clay with solutions of all the metals whose oxides are desiredprior to calcining the impregnated composition. Calcining of theimpregnated regenerated spent clay is conveniently accomplished byheating the impregnated regenerated spent clay to a temperature of fromabout 800 F. to 1000 F. in contact with an oxygen containing gas such asair to convert the metal compounds to the corresponding metal oxides.

HYDROCRACKING The reactions involved in the present process forconverting hydrocarbons to lower boiling hydrocarbons are primarily thecracking of the relatively heavy hydrocarbons and the hydrogenation ofunsaturated materials such as olefins, which may be present in thecharge stock or formed in the process, to saturated materials. Therelatively low boiling products can be separated into desired fractions,such as a gasoline fraction containing hydrocarbons having 4 carbonatoms up to those boiling at 400 F. (C4400 F.), a middle oil containinghydrocarbons boiling from 400 F. to 650 F., a heavy oil containinghydrocarbons boiling from 650 F. to 840 F., and recycle oil consistingof hydrocarbons boiling above 840 F. Other desired fractions can beseparated if desired.

A wide variety of heavy hydrocarbon materials having initial boilingpoints above about 840 F. can be converted in the process of theinvention, residues from petroleum cracking operations, reduced heavycrude oil, still tars, and the like, giving good results. It ispreferred to use heavy hydrocarbons having a hydrogen to carbon atomicratio of at least 1.2 and preferably above about 1.4. Good results areobtained when the A.P.I. gravity of the heavy hydrocarbons is below 25,but the process has its greatest utility when the A.P.I. gravity isbelow about 17. Generally the Ramsbottom carbon residue will be fromabout 9 to 30, but may be as low as about 4. It is preferred to usetower bottoms from petroleum opera/- tions, including for example theresidues from thermal or catalytic cracking operations, or reduced heavycrude oils including crude oils having a high content of sulfurcompounds, but other heavy hydrocarbon materials such as Athabasca tarcan be used. For convenience, the hydrocracking process of the inventionis herein described using residual oil as illustrative of the heavyhydrocarbon materials that can be employed.

In the hydrocracking process, the residual oil is contacted with acatalyst of the invention for from about 15 minutes to 8 hours at atemperature of from 700 F. to 925 F., and a pressure of from 400p.s.i.g. to 5000 p.s.i.g. Hydrogen must be present and preferably asubstantial excess is used, such as a mole ratio of hydrogen to 011 offrom 2 to 20. The process may be operated batchwise 'o'r continuously..lnbatch operation a catalyst to oil weight ratio of from 0.05 to 1gives good results.

In continuous operation, such as a fixed bed operation, a space rate ofoil through the reactor of from 0.2 to 6 volumes of oil per volume ofcatalyst per hour gives good results. Slurry type operation can also beemployed using reaction conditions essentiallyequivalent to those abovestated.

It is of primary importance, in operating the process, to relate thereaction conditions so that conversion of the hydrocarbon charge stockto material boiling below the boiling range of the, charge stock ismaintained below about 80% by weight for each contacting with thecatalyst. At higher conversions the production of coke and dry gasbecome excessive and deleteriously afiect the process. For an operableprocess, however, the conversion of the charge stock should be above 30%by weight for each contacting with catalyst.

After contacting the residual oil and catalyst under the conditions asstated above, the oil is separated into desired fractions bydistillation. A gasoline fraction can be separated and used as motorfuel, as a component of motor fuel by blending'with hydrocarbons fromother sources, or used in subsequent refinery operations such asreforming. Distillate oil products can be used without further treatmentsuch as for fuel oil, or can be used in subsequent refinery operationssuch as thermal or catalytic cracking. The higher boiling materials,generally the;hydrocarbons boiling above 840 F. provide excellentrecycle stock for the process since, as shown hereinafter, suchmaterials are upgraded in the process to contain a smaller quantity ofmaterials that are convertable to coke than is contained by the initialcharge material.

EXAMPLES In the following examples the regenerated spent clay wasprepared from an acid activated bentonite which had been used in aprocess for decolorizing a petroleum lubricating oil. When theadsorptive capacity of the clay for the non-hydrocarbon constituents ofthe lubricating oil. had been substantially depleted, the clay wasseparated "from the oil and the adherent oil removed by burni ng incontact with air. The resulting regeneratedspent clay contained fromabout 1% to 2% by weight carbon and impurities fromthe oil treatmentwhich were not removed in the burning step.

Example 1 A "catalytic composition was prepared in accordance with theinvention by impregnating the regenerated spent clay with an'aqueoussolution of 1.8 parts ofiammonium tungstate and 1.9 parts of ammoniummolybdate, in 250 parts of water. The concentration of the water solublecompounds and the quantity .of solution used were calculated to givedesired quantities of the metal oxides in the final composition. Theimpregnated composition was dried and heated to about 1000 F. in contactwith air. The resulting composition was screened to pass 100 mesh (U.S.series). The final catalytic composition contained 0.5% by Weight M00and 0.5% by weight W0 This composition is designated as catalyst A infollowing Table I.

The process used for the preparation of catalyst A was substantiallyrepeated except that, after impregnation with the aqueous solution ofthe molybdenum and tungsten compounds, a subsequent impregnation wasmade using an aqueous solution of nickelous nitrate. The solutioncontained 6 parts of Ni(NO -6H O in 50 parts of water. The concentrationof the nickelous nitrate and quantity of solution used'werecalculated-to give an equivalent quantity of nickel, i.e.,' a quantityof nickel just sufficient to react with the molybdenum and tungstencompounds. The resulting composition contained 0.5 by weight M00 0.5 byweight W0 and an equivalent quantity of nickel oxide. This compositionis designated as catalyst B in'followingTable I.

In a similar manner other catalytic compositions were prepared in whichother promoting oxides were substituted for nickel oxide. {These otherpromoting oxides were of the following metals, shown together with thedesignation of the final catalytic composition in Table I:

Catalyst designation It will be understood that each of the abovecatalytic compositions consisted essentially of regenerated spent clay,0.5% by weight molybdic oxide, 0.5% by weight tungsten oxide, and anequivalent quantity of the oxide of the indicated metal which, forexample, in catalyst C amounted to about 0.3% by Weight cobaltoxide(calculated as cobalt).

Each of the catalytic compositions were used to hydrocrack the sameresidual oil. The residual oil charge stock was from thevacuumdistillation of crude oil, and had an initial boiling point of about 840R, an A.P.I. gravity of 15.3, a Ramsbottom carbon residue of 9.3 byweight, a hydrogen to carbon atomic ratio of 1.60, and contained 0.77%by weight sulfur compounds (calculated as sulfur).

In carrying out the process, the indicated catalyst and residual oilwere introduced into a reactor, the catalyst to oil weight ratio being0.1. The reactor was flushed with hydrogen and hydrogen introduced to apressure of 2100 p.s.i.g., the hydrogen to oil mole ratio being about 6.The reactor was then heated and maintained at a temperature of 800 F.for 2 hours. After cooling, the catalyst was separated and thehydrocarbon reaction mixture distilled to separate desired fractions.The results obtained with the several catalysts are shown in followingTable I. In Table I, results obtained using regenerated spent clay,prepared aszabove described, as the catalyst are included forcomparison, the regenerated spent clay being designated as catalyst H.

TABLE I Catalyst desi nation Product distribution (wt. percent)" Dry gas(C1-C3) Gasoline {O -400 F.)

Heavy oil (650840 F.)

Recycle oil (above 840 F.) Ramsbottom Carbon Residue of Recycle oil (wt.percent) Coke (wt. percent) Charge converted (wt. percen Hydrogenconsumed (ft. /bbl.)

V Regenerated spent clay alone.

The data of Table I show good operation of the process of the inventionusing the catalysts of the invention. The good conversion of theresidual oil to distillate products, with only minor quantities of drygas and coke being formed, shows the effectiveness of the catalyticcompositions of the invention. It should be noted that with catalyticcompositions A through G, the Ramsbottom carbon residue of the recycleoil is less than the value for the charge stock. Hence the value of therecycle oil for reuse in the process is substantially enhanced in thateven better results are obtained therewith, and in that the oil can berecycled to substantial extinction, i.e., can be converted substantiallycompletely to lower boiling more valuable products.

The data obtained with catalyst H, which is not within the scope of thecatalytic compositions of the invention, show a degradation of therecycle oil as compared with the charge stock, and hence operationtherewith is unsatisfactory.

Example 2 To further illustrate catalytic compositions of the inventionand the necessity for using regenerated spent clay as a component of thecatalyst, a catalyst was prepared consisting essentially of 2% by weightM on regenerated spent clay (catalyst I). For comparison, a compositionconsisting essentially of 2% by weight M00 on coke was prepared(catalyst J). The coke was prepared by coking a petroleum residuum andhad an apparent density of 0.493, and was ground to pass 100 mesh. Also,a catalyst consisting essentially of M00 on bauxite (catalyst K) and acomposition consisting essentially of 5% M00 on a syntheticsilica-alumina cracking catalyst whose activity toward crackinghydrocarbons had been decreased about 30% by use in a hydrocarboncracking process (catalyst L) were prepared. To show the necessity ofusing molybdic oxide as a component of the catalytic compositions of theinvention, a composition consisting essentially of 1% by weight W0 onregenerated spent clay was prepared (catalyst M). The technique ofpreparation in each instance was substantially as described in Example1.

The residual oil charge stock, which had a Ramsbottom carbon residue of9.3% by Weight, and reaction conditions of temperature, pressure, time,hydrogen to oil mol ratio, and catalyst to oil weight ratio were asdescribed for Example 1. Results obtained are shown in following TableII:

TABLE II Catalytic Composition I J K L Product distribution (wt.percent):

Dry gas (Ci-Ca) Gasoline (Ct-400 F.) Middle Oil (400-650" F.) 11 Heavyoil (650840 F.) 24 Recycle oil (above 840 F.) 47

Ramsbottorn Carbon Residue of Recycle oil (wt. percent) Coke (wt.percent) Charge converted (wt. percent) 51 Hydrogen consumed (ft. /bbl.)

These data show that with catalytic composition I, within the scope ofthe invention, gave good results and upgraded the recycle oil, whereasthe remaining compositions, all of which are outside of the compositionsof the invention, caused degradation of the recycle oil.

Example 3 8 clay, coke fines obtained from the coking of coal. The cokewas screened to pass mesh (U.S. series). The compositions contained thefollowing indicated quantities, in percent by weight, of metal oxides:

Catalyst N2% MoO +1% Cr O Catalyst O2% MoO +1% Mn O Catalyst PO.5% MoO+0.5% W0 Catalyst Q-2% MoO +1% Fe 0 Each of these compositions were usedto hydrocrack the residual oil charge stock of Example 1, which had aRamsbottom carbon residue of 9.3%. The reaction conditions oftemperature, pressure, time, hydrogen to oil mol ratio, and catalyst tooil mol ratio were as described for Example 1. Results obtained areshown in following Table III:

TABLE III Catalytic Composition N Product distribution (wt. percent)-Dry gas (C1-C3) Gasoline (C4-400 F.) Middle oil (400-650 F.) Heavy oil(em-840 F.) Recycle oil (above 840 F.)

Ramsbottom Carbon Residue of Recycle oil (wt. percent) oke Chargeconverted (wt. percent) Hydrogen consumed (itfi/bbl.)

In like manner, an addition series of compositions were prepared using,in place of regenerated spent clay, coke obtained from the coking of apetroleum residuum at an elevated temperature. The coke was comminutedto pass 100 mesh. The compositions contained the following indicatedquantities, in percent by weight, of M00 and W0 and equivalentquantities of the indicated promoting oxides (calculated as theappropriate metal as above described):

Each of these compositions were used to hydrocrack the residual oilcharge stock of Example 1, which had a Ramsbottom carbon residue of9.3%. The reaction conditions of temperature, pressure, time, hydrogento oil mol ratio, and catalyst to oil mol ratio were as described forExample 1. Results obtained are shown in following Table IV: V

TABLE IV Catalytic Composition R S T U V W Product distribution (wt.percent):

Dry gas (Ci-C3) 4 4 3 6 4 4 Gasoline (CA-400 F.) 8 12 11 19 16 12 Middleoil (400650 F.) 14 14 26 19 19 17 Heavy oil (650-840" F.) 20 19 14 21 1921 Recycle oil (above 840 F.) 52 50 46 83 40 44 Ramsbottom CarbonResidue of Recycle oil (wt. percent).-- 11.1 10. 8 13.1 16. 2 15.0 11. 9Coke 0.5 0.8 0.3 1.2 1.7 0.6 Charge converted (wt. percent). 48 49 54 6558 54 Hydrogen consumed (tt. /bb1.).. 478 537 626 Still another seriesof compositions were prepared using bauxite in place of regeneratedspent clay. The bauxite was comminuted to pass 100 mesh. Thecompositions contained the following indicated quantities, in percent byweight; of metal oxides: "Catalys't X+1% MoO +Co (equivalent quantitycal- -culated as Co) t Catalyst .Y,-2% MoO +1% Cr 0 Catalyst Z-0.5% M0O+0.5% W0 An additional compositionwasprepared by depositing 0.5% by'weight M00 0.5% by weight W0 and an equivalent quantity (calculated asCo) of C0 0 on fresh Attapulgite, i.e. on a natural adsorbent clay whichhad not previously been used in a process involving contactinghydrocarbons therewith. This is designated as catalyst AA.

Each of these compositions was used to hydrocrack the residual oilcharge stock of Example 1, which had a Ramsbottom carbon residue of9.3%. The reaction conditions of temperature, pressure, time, hydrogento oil moi. ratio, and catalyst to oil mol. ratio were as described forExample 1. Results obtained are shown in following Table V:

TABLE V Catalytic Composition None of the compositions used in Example 3were within the scope of the invention, which requires regenerated spentclay as a catalytic component. Substituting other materials therefor, asshown by the data of the examples, defeats the objects of the inventionby causing degradation of the recycle fraction of the hydrocarbonproduct.

The catalytic compositions of the invention can be employed in processesother than hydrocracking, such as in desulfurization of crude oils,distillate oils, or residual oils. To obtain desulfurization it isadvantageous to contact the catalyst and oil, in the presence ofhydrogen, at relatively low temperatures, say from about 625 F. to 775F. and pressures of from about 400 p.s.i.g. to 5000 p.s.i.g. with a timeof contact sufiicient to achieve the desired degree of sulfur removal.

The foregoing examples illustrate embodiments of the invention. Whenother catalytic compositions within the scope of the invention areemployed, results substantially equivalent to those herein shown areobtained.

The invention claimed is:

'1. A new catalytic composition comprising regenerated spent clay andmolybdic oxide.

2. A new catalytic composition comprising regenerated spent clay havingdeposited thereon from 0.2% to 5% by weight molybdic oxide.

3. A new catalytic composition comprising regenerated spent clay, from0.2% to 5% by weight molybdic oxide and not above 5% by weight ofanother oxide of a metal selected from the group consisting of themetals of group VI(B) and of group VIII of the periodic table.

4. A new catalytic composition comprising regenerated spent clay, from0.2% to 5% by weight molybdic oxide and from 0.2% to 5% by weighttungsten oxide.

5. A new catalytic composition comprising regenerated spent clay, from0.2% to 5% by weight molybdic oxide and from 0.2% to 5% by weightchromium oxide.

6. A new catalytic composition comprising regenerated spent clay, from0.2% to 5% by weight molybdic oxide and from 0.2% to 5% by weight ironoxide.-

7. A new catalytic composition comprising regenerated ".10 spent clay,from 0.2% to"5%' by weight molybdic oxide and from 0.2% to 5% by weightcobalt oxid -8. A' newcatalytic composition comprising regenerated spentclayQfr'om' 0.2% to 5% 'by weightlm'olybdic oxide and from 0.2% to 5% byweight nickel oxide.

9. A new catalytic composition consisting essentially of regeneratedspent clay,from 0.2% to 5% by weight molybdic oxide, aquantity of notabove 5% by weight of another oxide of a metal selected from the groupconsisting of the metals of group VI-(B) and group VIII of the periodictable, and a promoting quantity of a promoting oxide.

10. A new catalytic composition according to claim 9 wherein saidpromoting oxide is an oxide of a metal selected from the groupconsisting of the metals of group VI(B) and group VIII of the periodictable, manganese and zinc.

11. A new catalytic composition consisting essentially of regeneratedspent clay, from 0.2% to 5% by weight molybdic oxide, from 0.2 to 5% byweight tungsten oxide, and an equivalent quantity of an oxide of a metalselected from the group consisting of chromium, iron, cobalt, nickel,manganese and zinc.

12. A new catalytic composition comprising regenerated spent clay havingdeposited thereon about 0.5% molybdic oxide, about 0.5% tungstic oxide,and an equivalent quantity of cobalt oxide.

13. A new catalytic composition comprising regenerated spent clay havingdeposited thereon about 0.5 molybdic oxide, about 0.5% tungstic oxide,and an equivalent quantity of iron oxide.

14. A new catalytic composition comprising regenerated spent clay havingdeposited thereon about 0.5% molybdic oxide, about 0.5% tungstic oxide,and an equivalent quantity of chromium oxide.

15. A new catalytic composition comprising regenerated spent clay havingdeposited thereon about 0.5% molybdic oxide, about 0.5% tungstic oxide,and an equivalent quantity of nickel oxide.

16. A new catalytic composition comprising regenerated spent clay havingdeposited thereon about 0.5% molybdic oxide, about 0.5% tungstic oxide,and an equivalent quantity of manganese oxide.

17. Process for converting hydrocarbons to lower boiling hydrocarbonswhich comprises contacting, in the presence of hydrogen, a mixture ofhydrocarbons boiling above about 840 F. with a catalytic compositioncomprising regenerated spent clay having deposited thereon from 0.2% to5% by weight molybdic oxide under reaction conditions including atemperature of from 700 F. to 925 F. and a presure of from 400 p.s.i.g.to 5000 p.s.i.g. to convert from 30% to by weight of the hydrocarbons tolower boiling hydrocarbons.

18. Process for converting hydrocarbons to lower boiling hydrocarbonswhich comprises contacting, in the presence of hydrogen, a mixture ofhydrocarbons boiling above about 840 F. with a catalytic compositioncomprising regenerated spent clay having deposited thereon from 0.2% to5% by weight molybdic oxide and a quantity of not above 5% by weight ofan oxide of a metal selected from the group consisting of the metals ofgroup VI(B) and group VIII of the periodic table under reactionconditions including a temperature of from 700 F. to 925 F. and apressure of from 400 p.s.i.g. to 5000 p.s.i.g. to convert from 20% to80% by weight of the hydrocarbons to lower boiling hydrocarbons.

19. Process according to claim 18 wherein said catalytic compositioncontains an equivalent quantity of an oxide of a metal selected from thegroup consisting of chromium, iron, cobalt(, nickel, manganese and zinc.

20. Process for the preparation of a novel catalytic composition whichcomprises contacting a natural adsorbent clay with hydrocarbons,separating the clay from the body of hydrocarbons, burning oil adheringto the clay to produce a regenerated spent clay containing from 1,1 1201. .to 4% by wei ht arbon im n t re- 2 Z 9 58 Sim on etal- -1- +1- O 20942 generated spent clay with 331 aqueqigs sghifion 01f awater 2,375,402Cbrson et a1. f. May '8, 1945 soluble pompound io f molybdenum, a 1 1 dheating the im-' 2,417,359 Guyer Mar. 11, '1947 pregnaied spent clay toa terflpenafcfite of frgm about 800 2,423,833 :Hirsh l "July 15, 1947=F. to 1000 F. in cpntaet with an oxygen containing gas. 5 2,457,566Krieger et a1 .-Dec; 28, 1948 0 2,687,370 Hendricks' Aug. 24, 1954References Cited in the file of this patent 2,700,014 Anhorn et a1. Jan.18, '1955 2,703,308 ,Oblad et a1 Mar. 1, 1955 UNITED STATES PATENTS21,77 ,247 Anhqni et a1. Jen. 1;, 1951 1,550,805 H a t er Aug. 25, 192510

17. PROCESS FORM CONVERTING HYDROCARBONS TO LOWER BOILING HYDROCARBONSWHICH COMPRISES CONTACTIG, IN THE PRESENCE OF HYDROGEN, A MIXTURE OFHYDROCARBONS BOILING ABOVE ABOUT 840*F. WITH A CATALTIC COMPOSITIONCOMPRISING REGENERATED SPENT CLAY HAING DEPOSITED THEREON FROM 0.2% TO5% BY WEIGHT MLYBDIC OXIDE UNDER REACTION CONDITIONS INCLUDING ATEMPERATURE OF FROM 700* F. TO 925*F. AND A PRESSURE OF FROM 400P.S.I.G. TO 5000 P.S.I.G. TO CONVERT FROM 30% TO 80% BY WEIGHT OF THEHYDROCARBONS TO LOWER BOILING HYDROCRBONS.